CN108369363A

CN108369363A - Electrochromic device

Info

Publication number: CN108369363A
Application number: CN201780004513.1A
Authority: CN
Inventors: 姜铢熙; 章盛皓; 金忠完
Original assignee: LG Chemical Co Ltd
Current assignee: LG Chem Ltd; LG Corp
Priority date: 2016-03-08
Filing date: 2017-03-08
Publication date: 2018-08-03
Anticipated expiration: 2037-03-08
Also published as: KR102010753B1; US20180373108A1; US10877348B2; CN108369363B; KR20170104944A

Abstract

Method this application involves electrochromic device and for manufacturing electrochromic device.The application can provide the electrochromic device with the productivity and improved electrochromism rate and durability improved and the method for manufacturing electrochromic device.The electrochromic device may be advantageously used with various devices, such as smart window, smart mirror, display, Electronic Paper and adaptive camouflage.

Description

Electrochromic device

Technical field

This application involves the purposes of electrochromic device and the electrochromic device.

This application claims based on March 8th, 2016 South Korea patent application submitted the 10-2016-0027597th and In on March 7th, 2017 South Korea patent application submitted the 10-2017-0028748th priority equity, the disclosure of which It is incorporated herein by reference in their entirety.

Background technology

Electrochromism refers to the optical characteristics such as color or transmissivity of electrochromic activity material by the electrochemistry oxygen of material Change the phenomenon that reduction reaction is changed.Being manufactured into small cost using the electrochromic device of this phenomenon is had The device of large area and have low energy consumption so that it can be used for various fields, such as smart window, smart mirror and Electronic Paper (patent document 1：South Korea speciallys permit patent disclosure the 2008-0051280th).

As electrochromic material, transition metal oxide may be exemplified.For example, WO₃、MoO₃、TiO₂Etc. may be exemplified for Pass through the colour development material and LiNiOx, NIOx, V of reduction₂O₅、IrO₂Etc. may be exemplified as by the colour development material of oxidation.

In order to which electrochromic material is applied to electrochromic device, it is desirable to provide the electrochromic material of form of film. In an example, sputtering vacuum equipment can be used to keep electrochromic material thinning.However, vacuum deposition method has high list First process costs and maintenance cost, although and being hundreds of nanometers thin in order to which stabilized driving electrochromic device needs thickness Film, but the deposition rate of vacuum deposition method is low, thus there are problems that being difficult to be applied to large-scale production.As vacuum There is the method for coating electrochromic material in the replacement of deposition method.Cladding process has simple work compared with vacuum deposition method Skill, therefore have the effect of reducing process costs, but since the adhesiveness between coating and base material reduces, volume may be also needed to Outer technique such as treatment process.

On the other hand, in electrochromic device field, need to keep stable electrochromism spy during loop test Property and have thermal stability and durability.In addition, when electrochromic device deteriorates, reduced there are electrochromic property or The problem of cannot achieve and observing visually deterioration, therefore, it is necessary to improve electrochromism stability to use it for smart window Deng.

Invention content

Technical problem

The application target to be solved is to provide the electroluminescent change with improved productivity, electrochromism rate and durability Color device with improve electrochromic device productivity and solve and compensation the process stabilizing sex chromosome mosaicism caused by material, and Method for manufacturing the electrochromic device.

Technical solution

This application involves electrochromic devices.The electrochromic device of the application can include first electrode layer successively, compound Electrochromic layer, electrolyte layer, ion storage and the second electrode lay.Composite electrochromic layer may include multiple electrochromic layers Laminate structures.At least two electrochromic layers in multiple electrochromic layers can have different density.With difference The higher electrochromic layer of density in two electrochromic layers of density can be configured to and the lower electrochromic layer of density Compared to closer first electrode layer.First electrode layer and the second electrode lay can be separately positioned in the first substrate and the second substrate.

The electrochromic device of the application can be realized by the relatively small electrochromic layer laminate structures of thickness so that Productivity can be improved.In addition, the electrochromic device of the application can be by via the different multiple electroluminescent changes of layout density Chromatograph prevents the ion in electrolyte layer (for example, Li⁺Ion) penetrate into electrode layer in come reduce because electrode layer material (for example, ITO degradation phenomena caused by the side reaction of the ion) and in electrolyte layer, to show excellent electrochromism rate and resistance to Long property.

Fig. 1 schematically shows the electrochromic device of an embodiment according to the application.As shown in Figure 1, root Electrochromic device according to one embodiment of the invention can include the first substrate (10) successively, first electrode layer (11), answer Close electrochromic layer (12), electrolyte layer (3), ion storage (22), the second electrode lay (21) and the second substrate (20).It is compound Electrochromic layer (12) may include at least two electrochromic layers (121,122) with different densities, and density is higher First electrochromic layer (121) can be configured to lower second electrochromic layer of specific density closer to first electrode layer (11). In the electrochromic device according to Fig. 1, higher first electrochromic layer (121) of density is adjacent with first electrode layer (11), And lower second electrochromic layer (122) of density is adjacent with electrolyte layer (3).

Hereinafter, the electrochromic device of the application will be described in detail.

[electrode layer]

In the present specification, the electrode layer adjacent with composite electrochromic layer is referred to alternatively as first electrode layer, and with from The adjacent electrode layer of sub- accumulation layer is referred to alternatively as the second electrode lay.First electrode layer and the second electrode lay can be used for compound electroluminescent Photochromic layer or ion storage supply charge.First electrode layer is referred to alternatively as while adjacent with composite electrochromic layer in electricity Cause the adjacent electrode with electrochromism effect in color-changing device, such as active electrode.The second electrode lay be referred to alternatively as with from Sub- accumulation layer can accommodate the electrode of the hydrogen desorbed from active electrode or lithium ion etc. while adjacent, such as to electrode.However, As described below, when ion storage also includes electrochromic material, both first electrode layer and the second electrode lay are available Make to be used as active electrode simultaneously to electrode.

First electrode layer and the second electrode lay respectively may include transparent conductive material.Specifically, first electrode layer and second Electrode layer respectively may include at least one of transparent conductive oxide, conducting polymer, nano silver wire and metal mesh.At one In example, as transparent conductive oxide, it can use that ITO (tin indium oxide), FTO (tin oxide of Fluorin doped), AZO (mix by aluminium Miscellaneous zinc oxide), the GZO zinc oxide of doping (gallium), ATO (tin oxide of Sb doped), IZO (zinc oxide of indium doping), NTO (titanium oxide of niobium doping), ZnO or CTO etc., but not limited to this.In another example, first electrode layer and the second electrode lay It can be formed as the wherein laminated structure for having two or more materials in above-mentioned transparent conductive oxide.

First electrode layer or the second electrode lay can be manufactured for example by following procedure：By such as sputter or number print The technique of brush forms the electrode material for including transparent conductive oxide particle in the form of a film in clear glass substrate.

First electrode layer or the physical characteristic of the second electrode lay can be appropriate in the range of not damaging the purpose of the application Ground is adjusted.In an example, first electrode layer or the second electrode lay be designed to have low thickness and sheet resistance with And high transmissivity.The sheet resistance of first electrode layer or the second electrode lay is lower, and the coloring and decoloration of electrochromic device turn The time is changed more to tend to reduce.In consideration of it, the physics that can suitably control first electrode layer or the second electrode lay is special Property.For example, the thickness of first electrode layer or the second electrode lay can be 1nm to 500nm.

The voltage applied to first electrode layer or the second electrode lay by external circuit can be in the purpose for not damaging the application In the range of suitably adjust.The voltage applied to first electrode layer or the second electrode lay is higher, the characteristic of electrochromic device It is better, but may be deteriorated by accelerator by durability is made to reduce.In consideration of it, can be suitably adjusted by outer The voltage that circuit applies first electrode layer or the second electrode lay.For example, by external circuit to first electrode layer or second electrode The voltage that layer applies can be -5V to+5V, but not limited to this.In addition, voltage when coloring and decoloration can be identical or different, And if desired, can suitably be adjusted.Voltage can be applied by AC power, and apply alive power supply Or method can be properly selected by those skilled in the art.

As shown in Figure 1, the electrochromic device of the application, which may also include, is separately positioned on first electrode layer and second electrode The first substrate and the second substrate on one surface of layer.First substrate and the second substrate can be respectively substrate of glass or polymerization Object substrate.Specifically, each of the first substrate and the second substrate can be it is selected from the following any one：Glass, glass fibre, Polyethylene terephthalate, polyethylene naphthalate, makrolon, polyether sulfone, polyimides and combinations thereof.According to The embodiment of the application, the first substrate can be substrate of glass, and the second substrate can be polymeric substrates.

[composite electrochromic layer]

Composite electrochromic layer can be with the laminate structures of multiple electrochromic layers.In the present specification, multiple electroluminescent changes The laminate structures of chromatograph can refer to the laminate structures of at least two electrochromic layers.In the present specification, about electrochromic layer, Unless it is defined as " compound " or " multiple ", otherwise electrochromic layer can refer to the single electrochromic layer being individually formed.Such as Fruit needs, composite electrochromic layer can have there are two, the laminate structures of three, four, five or more electrochromic layers.

The density of at least two electrochromic layers in multiple electrochromic layers can be different from each other.Density it is different two The higher electrochromic layer of density in a electrochromic layer can be arranged to the lower electrochromic layer of specific density closer to One electrode layer.By preventing the ion in electrolyte layer (for example, Li via above-mentioned arrangement⁺Ion) electrode layer is penetrated into, it can subtract Few degradation phenomena caused by the side reaction of the ion in electrode layer material (for example, ITO) and electrolyte layer, it is excellent to show Different electrochromism rate and durability.

In an example, when composite electrochromic layer has the laminate structures of two different electrochromic layers of density When, the higher electrochromic layer of density can be configured to adjacent with first electrode layer, and the lower layer of density can be configured to It is adjacent with electrolyte layer.In another example, when composite electrochromic layer have density it is different three or more are electroluminescent When the laminate structures of photochromic layer, the highest electrochromic layer of density can be configured to adjacent with first electrode layer, and density is most Low electrochromic layer can be configured to adjacent with electrolyte layer.In addition, electrochromic layer can be disposed so that electrochromism The density of layer becomes lower from first electrode layer side to electrolyte layer side.

Multiple electrochromic layers may be arranged so that at least two different electrochromic layers of such as density are adjacent to each other. Therefore, according to the electrochromic device of the application, at least two different electrochromic layers of density can be with shape adjacent to each other State is driven.

At least two different electrochromic layers of multiple electrochromic layers such as density can be laminated directly with one another.In this explanation In book, phrase " A and B are laminated directly with one another " can refer to that middle layer such as pressure-sensitive adhesive layer or adhesive layer are not present between A and B In the case of A and B it is laminated each other.Two or more electrochromic layers it is direct it is laminated can be for example by an electroluminescent change Another electrochromic layer is deposited or coated on chromatograph to carry out.

In view of the purpose of the application, the density contrast of two different electrochromic layers of density can be properly selected. In one example, density contrast can be 0.1g/cm³Or bigger, 0.2g/cm³Or bigger, 0.3g/cm³Or bigger, 0.4g/cm³Or Bigger or 0.5g/cm³Or bigger.The upper limit of density contrast can be 3.0g/cm³Or smaller.When density different two is electroluminescent The density contrast of photochromic layer in the above range when, with raising productivity and realize with excellent electrochromism rate It can be advantageous with the electrochromic device aspect of durability.

In view of the purpose of the application, two different respective density of electrochromic layer of density can be properly selected. In an example, the density of the higher electrochromic layer of density in two different electrochromic layers of density can be 5.0g/cm³To 8.0g/cm³.Specifically, the density of the higher electrochromic layer of density can be 5.0g/cm³Or bigger, 5.25g/cm³Or bigger, 5.5g/cm³Or bigger, 5.75g/cm³Or bigger, 6g/cm³Or bigger or 6.25g/cm³Or bigger And 8.0g/cm³Or smaller, 7.5g/cm³Or smaller, 7.0g/cm³Or smaller or 6.5g/cm³Or smaller.It is different in density The density of the lower electrochromic layer of density in two electrochromic layers can be 3.0g/cm³To 7.0g/cm³.Specifically, close The density for spending lower electrochromic layer can be 3.0g/cm³Or bigger, 3.5g/cm³Or bigger, 4.0g/cm³Or bigger, 4.5g/cm³Or bigger or 5.5g/cm³Or bigger and 7.0g/cm³Or smaller, 6.5g/cm³Or smaller or 6.0g/cm³Or Smaller.When the density of each electrochromic layer in the above range when, with raising productivity and realize with excellent It can be advantageous in terms of the electrochromic device of electrochromism rate and durability.

In view of the purpose of the application, each electrochromic layer being included in composite electrochromic layer can be properly selected Thickness.In an example, the thickness of each electrochromic layer can be respectively 10nm to 800nm.Specifically, in density difference Two electrochromic layers in, the thickness of the higher electrochromic layer of density can be 10nm to 800nm, and density is lower The thickness of electrochromic layer can be 10nm to 800nm.More specifically, the thickness of the higher electrochromic layer of density can be 10nm or bigger, 20nm or bigger, 30nm or bigger, 60nm or bigger or 90nm or bigger and 400nm or smaller, 300nm Or smaller, 200nm or smaller or 100nm or smaller.More specifically, the thickness of the lower electrochromic layer of density can be 10nm or bigger, 50nm or bigger, 100nm or bigger, 150nm or bigger and 400nm or smaller, 300nm or smaller or 200nm or smaller.In addition, the overall thickness of composite electrochromic layer can be 20nm to 810nm.More specifically, compound electric mutagens The overall thickness of chromatograph can be 20nm or bigger, 60nm or bigger, 100nm or bigger, 140nm or bigger, 180nm or bigger and 810nm or smaller, 700nm or smaller, 600nm or smaller, 500nm or smaller, 400nm or smaller or 300nm or smaller. When the thickness of composite electrochromic layer meets range above, with raising productivity and realize with excellent electroluminescent It can be advantageous in terms of the electrochromic device of discoloration rate and durability.

At least two different electrochromic layers of density can be realized by different physical arrangements.In an example, Different any one of at least two electrochromic layers of density can be perforated membrane.In a specific example, density not With at least two electrochromic layers in the lower electrochromic layer of density can be with compared with the higher electrochromic layer of density It is perforated membrane.In the present specification, perforated membrane can refer to the film with porous structure, that is, the film having a structure in which, wherein There are multiple holes (porosity) on the inside or surface of the film.In the present specification, phrase " A is perforated membrane compared with B " can Mean that A ratios B includes more holes.

At least two different electrochromic layers of multiple electrochromic layers such as density respectively may include electrochromic material. Electrochromism is the phenomenon that color reversibly changes according to electric signal, and electrochromism can be by electrochromic material Insertion/extraction electronics and ion (H⁺、Li⁺Deng) process and occur.Electrochromic material can be divided into reversible by ion implanting The reproducibility electrochromic material of ground coloring and the oxidisability electrochromic material reversibly coloured by the ion extraction.

As electrochromic material, metal oxide electrochromic material, metal complex compounds, organic can be used Electrochromic material or conducting polymer electrochromic material etc..

As the example of metal oxide electrochromic material, tungsten (W), titanium (Ti), vanadium (V), molybdenum (Mo), niobium can be used (Nb), the metal oxide of chromium (Cr), manganese (Mn), tantalum (Ta), iron (Fe), nickel (Ni), cobalt (Co), iridium (Ir) and lithium nickel (LiNi) In one or more.The metal oxide of tungsten (W), titanium (Ti), vanadium (V), molybdenum (Mo), niobium (Nb) etc. can be classified as also Originality electrochromic material, and vanadium (V), chromium (Cr), manganese (Mn), tantalum (Ta), iron (Fe), nickel (Ni), cobalt (Co), iridium (Ir) or Lithium nickel (LiNi) etc. can be classified as oxidisability electrochromic material.

As metal complex compounds, it is, for example, possible to use Prussian blue, phthalocyanine or bismuth etc..

As organic electrochromic material, it is, for example, possible to use viologen or quinone etc..

As conducting polymer electrochromic material, it is, for example, possible to use one or more below：Polythiophene gathers Aniline, polypyrrole, poly- anthracene, polyfluorene, polycarbazole, polyphenylene vinylene and its derivative.

In an example, at least two different electrochromic layers of multiple electrochromic layers such as density respectively may include The electrochromic material of identical type.As an example, at least two different electrochromic layers of density respectively may include tungsten Oxide (WOx).The electrochromic device of the application is implemented so that at least two of the electrochromic material comprising identical type The density of a electrochromic layer is different from each other, it is possible thereby to improve the productivity of electrochromic device, and can solve and mend It repays by the process stabilizing sex chromosome mosaicism caused by material.

[ion storage]

Ion storage can be used for receiving and release causes ionic charge necessary to electrochromic layer discoloration.Therefore, it is Charge balance between matching ion storage and electrochromic layer, ion storage may include and electrochromic layer is complementary Conductive material.

When composite electrochromic layer includes reproducibility electrochromic material, ion storage may include oxidisability conduction material Material.Alternatively, when composite electrochromic layer includes oxidisability electrochromic material, ion storage may include reproducibility conduction material Material.

As an example, the conductive material included in ion storage can be electrochromic material.Work as compound electric When mutagens chromatograph includes reproducibility electrochromic material, ion storage may include oxidisability electrochromic material.Work as compound electric When mutagens chromatograph includes oxidisability electrochromic material, ion storage may include reproducibility electrochromic material.According to this Shen An embodiment please, when in composite electrochromic layer use tungsten oxide (WO₃) when, it can make in ion storage With lithium nickel oxide (LiNixOy).

Alternatively, no matter composite electrochromic layer includes reproducibility off-color material or oxidisability off-color material, ion storage Layer also may include suitable conductive material, such as the conductive material of such as electrically conductive graphite.

The thickness of ion storage can properly select in the range of not damaging the purpose of the application.For example, ion The thickness of accumulation layer can be 20nm to 810nm.When the thickness of ion storage meets range above, can provide with changing The electrochromic device of kind electrochromism rate and stability.

[electrolyte layer]

Electrolyte layer may include electrolytic salt.Specifically, electrolyte layer can be it is selected from the following any one：Wherein dissolve There are liquid electrolyte, gel electrolyte, solid electrolyte, polymer dielectric and the gel polymer electrolyte of electrolytic salt. In the case of liquid electrolyte, it can be the wherein liquid electrolyte of dissolving electrolyte salt in a solvent.According to the application An embodiment, electrolyte can be gel polymer electrolyte.

Electrolytic salt can be organic electrolytic salt or inorganic electrolyte salt.More specifically, electrolytic salt may include lithium salts, Sylvite, sodium salt or ammonium salt etc., and electrolytic salt can be for example it is selected from the following any one：n-Bu₄NClO₄、n-Bu₄NPF₆、 NaBF₄、LiClO₄、LiPF₆、LiBF₄、LiN(SO₂C₂F₅)₂、LiCF₃SO₃、C₂F₆LiNO₄S₂、K₄Fe(CN)₆And combinations thereof.

If solvent be non-aqueous solvent if can apply, specifically, solvent can be it is selected from the following any one：Dichloromethane Alkane, chloroform, acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), tetrahydrofuran (THF), butylene carbonate and combinations thereof.

The thickness of electrolyte layer can properly select in the range of not damaging the purpose of the application.For example, electrolyte The thickness of layer can be 400nm to 2000nm.When the thickness of electrolyte layer meets range above, can provide with improvement The electrochromic device of electrochromism rate and stability.

The application further relates to the method for manufacturing electrochromic device.The manufacturing method can be for manufacturing above-mentioned electricity The method for causing color-changing device.The manufacturing method may include in first electrode layer laminated composite electrochromic layer, electrolyte successively The process of layer, ion storage and the second electrode lay.In this manufacturing method, composite electrochromic layer may include multiple electroluminescent changes Chromatograph, wherein the density of at least two electrochromic layers in multiple electrochromic layers is different from each other, and in density difference Two electrochromic layers in the higher electrochromic layer of density can be laminated compared with the lower electrochromic layer of density with It is arranged to adjacent with first electrode layer.In this manufacturing method, first electrode layer, composite electrochromic layer, electrolyte layer, from Sub- accumulation layer and the details of the second electrode lay can be equally applied by the content described in the project in electrochromic device.

In this manufacturing method, interlayer laminating method can be carried out by properly selecting known method.In a reality In example, each layer can be formed using following any method：Sputtering, sol-gel method, electron beam evaporation plating (e-beam Evaporation), pulsed laser deposition, CVD (chemical vapor deposition), spin coating and dip-coating.

In this manufacturing method, the Auto-regulating System of Density of Heavy Medium of at least two electrochromic layers can be passed through into such as lower section at different from each other Formula carries out：Laminated is in any electrochromic layer of porous form membrane compared with other adjacent electrochromic layers.The details of perforated membrane It can be equally applied by the content described in the project in electrochromic device.

In an example, in laminated electrochromic layer, the electrochromic layer of laminated porous film form can be by right It is carried out using sputtering technology, and condition is adjusting operation pressure condition, or by being applied to electron beam evaporation plating (E-beam Evaporation) technique carries out, and condition is to adjust gas condition.Operation pressure condition or electron beam in sputtering technology is heavy Gas condition in product technique can be properly selected according to the density to be realized.

As an example, when application sputtering technology, as operation pressure increases, the density of electrochromic layer is tended to Reduce.Alternatively, when applying electronic beam evaporation process, increase operation pressure with being injected by gas, electrochromic layer it is close Degree tends to reduce.On the other hand, since sputtering technology source is the rigid solid of metal component and electron beam evaporation source It is granule type solid, therefore since that there may be density is different about technique for sputtering source and electron beam evaporation plating source difference.

The electrochromic device of the application has the effect of improving electrochromism rate and stability.Such electrochromism Device may be advantageously used with various devices, such as smart window, smart mirror, display, Electronic Paper and adaptive camouflage (adaptive camouflage).The method of the such device of construction is not particularly limited, as long as using the electroluminescent change of the application Color device can apply conventional method.

Advantageous effect

The application can provide the electroluminescent change with the productivity and improved electrochromism rate and durability that improve Color device.Such electrochromic device may be advantageously used with various devices, such as smart window, smart mirror, display, electronics Paper and adaptive camouflage.

Description of the drawings

Fig. 1 schematically shows the electrochromic device of an embodiment according to the application.

Fig. 2 to 5 is the map of current of embodiment 1 to 3 and comparative example 1 respectively.

Fig. 6 is coloring and decoloration figure under embodiment 1 is recycled at the 750th time.

Fig. 7 is coloring and decoloration figure under embodiment 2 is recycled at the 750th time.

Fig. 8 is the color-patch map under embodiment 3 is recycled at the 400th time.

Fig. 9 to 11 is the charge spirogram of embodiment 1 to 3 respectively.

Figure 12 to 14 is the transmissivity and charge spirogram of embodiment 1 to 3 respectively.

Figure 15 to 16 is the charge spirogram of embodiment 2 and comparative example 2 respectively.

Figure 17 is the color-patch map under comparative example 2 is recycled at the 50th time.

Figure 18 is the transmissivity and charge spirogram of comparative example 2.

Specific implementation mode

Hereinafter, present context will be more fully described by embodiment and comparative example, but scope of the present application is not It is limited to the following contents.

Measure embodiment 1

Using XRR (X ray reflection) analytic approach, every 0.002 degree of 2 θ from 0.2 degree to 2.4 degree measure electrochromic layer in 1 second Density of film.

1 (stacked body of embodiment：Glass/ITO/WOx (1)/WOx (2)/GPE/LiNixOy/ITO/PET films)

The manufacture of working electrode

The first electrochromic layer (121) is formed by following procedure：Pass through in laminated ITO layer on the glass substrate Plasma is formed on W (tungsten) target using DC sputters, and by Ar and O₂In gas flood chamber, pass through active reaction so that Form of film with thickness for about 30nm provides WOx (tungsten oxide).With the high pressure of 6.03kV and 0.5nm/ seconds evaporation rates The sources WOx are set, the second electrochromic layer (122) is formed on the first electrochromic layer (121) by electron beam evaporation plating so that with Thickness provides WOx (tungsten oxide) for the form of film of about 150nm.The density of first electrochromic layer (121) is about 6.3 ± 0.1g/cm³And second the density of electrochromic layer (122) be about 5.8 ± 0.1g/cm³。

Manufacture to electrode

Ion storage (22) is formed by following procedure：DC sputters are used in laminated ITO layer on a pet film In LiNiO₂Form plasma on target, and by Ar and O₂In gas flood chamber, pass through active reaction so that with thickness be about The form of film of 75nm provides LiNixOy.

The manufacture of electrochromic device

Using including PC (propylene carbonate) and LiClO₄Mixture gel polymer electrolyte, pass through the electricity that will work Pole and the second electrochromic layer (122) and ion storage (21) and gel polymer electrolyte are joined together such that electrode (3) it contacts to manufacture electrochromic device.

2 (stacked body of embodiment：Glass/ITO/WOx (1)/WOx (2)/GPE/LiNixOy/ITO/PET films)

Electrochromic device is manufactured in the same manner as in example 1, the difference is that, it is formed in embodiment 1 When the first electrochromic layer (121), provided come the form of film with thickness for about 60nm by increasing DC sputtering times twice First electrochromic layer (121).The density of first electrochromism layer film (121) is about 6.3 ± 0.1g/cm³And second electricity The density of mutagens chromatograph film (122) is about 5.8 ± 0.1g/cm³。

3 (stacked body of embodiment：Glass/ITO/WOx (1)/WOx (2)/GPE/LiNixOy/ITO/PET films)

Electrochromic device is manufactured in the same manner as in example 1, the difference is that, it is formed in embodiment 1 When the first electrochromism layer film (121), by the way that DC sputtering times are increased three times come with form of film that thickness is about 90nm First electrochromism layer film (121) is provided.The density of first electrochromism layer film (121) is about 6.3 ± 0.1g/cm³, with And second the density of electrochromism layer film (122) be about 5.8 ± 0.1g/cm³。

1 (stacked body of comparative example：Glass/ITO/WOx/GPE/LiNixOy/ITO/PET films)

Electrochromic device is manufactured in the same manner as in example 1, the difference is that, it manufactures in embodiment 1 Working electrode and when forming the first electrochromism layer film (121), is about with thickness by increasing by 14 times of DC sputtering times The single film layer structure of 420nm forms electrochromic layer.The density of electrochromism layer film is about 6.3 ± 0.1g/cm³。

2 (stacked body of comparative example：Glass/ITO/WOx (2)/WOx (1)/GPE/LiNixOy/ITO/PET films)

Electrochromic device is manufactured in a manner of in the same manner as in Example 2, the difference is that, it manufactures in example 2 When working electrode, it is about 5.8 ± 0.1g/cm to form density first in ITO electrode layer³The second electrochromic layer (122), so It is about 6.3 ± 0.1g/cm to form density on the second electrochromic layer (122) afterwards³The first electrochromic layer (121).

The driving and deterioration assessment of electrochromic device

Drive the electrochromic device manufactured in embodiment and comparative example to assess the presence of deterioration under the following conditions, knot Fruit is shown in Fig. 2 to 9.

Drive bias：The AC voltages of -2V to+2V

Duration：100 seconds (coloring) -100 seconds (decoloration).

Fig. 2 to 5 respectively illustrates the electric current of the electrochromic device of embodiment 1 to 3 and comparative example 1 in coloring and decoloration Measure the variation according to elapsed time and cycle-index.As shown in Fig. 2 to 5, in comparative example 1, after deterioration is recycled at 100 times Occur, and in Examples 1 and 2, it is not deteriorated even if at 800 times under cycle or more time cycle, in embodiment 3, Up to about 150 times cycle just deteriorates, thus may determine that, embodiment 3 has more preferably durability compared with comparative example 1. Fig. 7 and 8 is coloring and decoloration figure of the electrochromic device of Examples 1 and 2 after 750 cycles of driving, and Fig. 9 respectively It is color-patch map of the embodiment 3 after 400 cycles of driving.In embodiment 3, it is deteriorated under being recycled at the 400th time, and Aberration is not present between coloring and decoloration.Fig. 9 to 11 respectively illustrates the electroluminescent change of the embodiment 1 to 3 in coloring and decoloration The quantity of electric charge of color device is according to the variation of elapsed time.When the quantity of electric charge increases, it may imply that Li+ ions are remarkably contributing to Color and decoloration or electrochromism.As shown in figs. 9 and 11, it may be determined that in the case of Examples 1 and 2, follow for up to about 750 times Ring, electrochromic device show stable electrochromic property, and the quantity of electric charge does not reduce.Figure 12 to 14 respectively illustrate The transmissivity of the electrochromic device of embodiment 1 to 3 and the quantity of electric charge are according to the variation of cycle-index when color and decoloration.

Figure 15 to 16 respectively illustrates the charge of the electrochromic device of embodiment 2 and comparative example 2 in coloring and decoloration Measure the variation according to elapsed time.As shown in Figure 15 to 16, it may be determined that in example 2, electrochromic device is shown Stable electrochromic property, the quantity of electric charge are not reduced according to elapsed time, and in comparative example 2, electricity after being recycled at 50 times Lotus amount reduces.Figure 17 is color-patch map of the comparative example 2 after 50 cycles of driving.In comparative example 2, after 50 cycles of driving It deteriorates, and there is no aberration between coloring and decoloration.Figure 18 shows the electroluminescent change of the comparative example 2 in coloring and decoloration The transmissivity and the quantity of electric charge of color device are according to the variation for following number.

[reference sign]

10：First substrate, 11：First electrode layer, 12：Composite electrochromic layer, 122：Second electrochromic layer, 121：The One electrochromic layer, 20：Second substrate, 21：The second electrode lay, 22：Ion storage, 3：Electrolyte layer.

Claims

1. a kind of electrochromic device includes first electrode layer, composite electrochromic layer, electrolyte layer, ion storage successively And the second electrode lay, wherein the composite electrochromic layer includes the laminate structures of multiple electrochromic layers, in the multiple electricity At least two electrochromic layers in mutagens chromatograph have density different from each other, and with described in different densities at least The higher electrochromic layer of density in two electrochromic layers is configured to the lower electrochromic layer of specific density closer to institute State first electrode layer.

2. electrochromic device according to claim 1, wherein described two electrochromic layer quilts with different densities It drives adjacent to each other.

3. electrochromic device according to claim 1, wherein described two electrochromic layers with different densities that This is directly laminated.

4. electrochromic device according to claim 1, wherein described two electrochromic layers with different densities Density contrast is 0.1g/cm³Or bigger.

5. electrochromic device according to claim 1, wherein the density of the higher electrochromic layer of the density is 5.0g/cm³To 8.0g/cm³。

6. electrochromic device according to claim 1, wherein the density of the lower electrochromic layer of the density is 3.0g/cm³To 7.0g/cm³。

7. electrochromic device according to claim 1, wherein in described two electrochromic layers with different densities Each thickness be 10nm to 800nm.

8. electrochromic device according to claim 1, wherein the lower electrochromic layer of the density and the density It is perforated membrane that higher electrochromic layer, which is compared,.

9. electrochromic device according to claim 1, wherein in described two electrochromic layers with different densities Each include tungsten (W), titanium (Ti), vanadium (V), molybdenum (Mo), niobium (Nb), chromium (Cr), manganese (Mn), tantalum (Ta), iron (Fe), nickel (Ni), at least one of metal oxide of cobalt (Co), iridium (Ir) and lithium nickel (LiNi) metal oxide.

10. electrochromic device according to claim 1, wherein in described two electrochromic layers with different densities Each include the electrochromic material of identical type.

11. electrochromic device according to claim 1, wherein when the composite electrochromic layer includes that reproducibility is electroluminescent When off-color material, the ion storage includes oxidisability conductive material, or when the composite electrochromic layer includes oxidation Property electrochromic material when, the ion storage include reproducibility conductive material.

12. electrochromic device according to claim 1, wherein the electrolyte layer includes electrolytic salt and described Electrode layer includes transparent conductive material.

13. a kind of method for manufacturing electrochromic device according to claim 1, including in first electrode layer according to The process of secondary laminated composite electrochromic layer, electrolyte layer, ion storage and the second electrode lay, wherein the compound electric mutagens Chromatograph includes the laminate structures of multiple electrochromic layers, at least two electrochromic layers tool in the multiple electrochromic layer Have density different from each other, and tegillum synthesize so that density in described two electrochromic layers with different densities compared with High electrochromic layer is configured to adjacent with the first electrode layer compared with the lower electrochromic layer of density.

14. the method according to claim 13 for manufacturing electrochromic device, wherein by the multiple electrochromism The Auto-regulating System of Density of Heavy Medium of layer carries out in the following way at different from each other：In laminated the multiple electrochromic layer with another arbitrary electricity Mutagens chromatograph compares any electrochromic layer in porous form membrane.

15. the method according to claim 14 for manufacturing electrochromic device, wherein laminated is in porous form membrane The electrochromic layer is carried out by being applied to sputtering technology, and condition is adjusting operation pressure condition, or by it Applying electronic beam evaporation process carries out, and condition is to adjust gas condition.